Lower alkyl ether-containing disazo dyes for nylon

ABSTRACT

Compounds of the formula   WHEREIN A is hydrogen, lower alkyl, such as methyl, ethyl, butyl or lower alkoxy, such as methoxy, ethoxy, butoxy, or chlorine; B is hydrogen, lower alkyl such as methyl, ethyl or butyl or lower alkoxy, such as methoxy, ethoxy or butoxy; B1 is lower alkoxy such as methoxy, ethoxy or butoxy; E1 is hydrogen, lower alkyl such as methyl, ethyl, butyl or lower alkoxy such as methoxy, ethoxy or butoxy, E2 is hydrogen, lower alkyl such as methyl or ethyl, lower alkoxy such as methoxy or ethoxy; R is lower alkyl of 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl and OR is either ortho or para to the azo linkage; and -SO3H is either meta or para to A, provide yellow to scarlet dyeings of very good fastness and dyeing properties and excellent leveling characteristics on natural and synthetic polyamide fibers.

United States Patent [1 1 Stingl [451 Jan. 21, 1975 LOWER ALKYL ETHER-CONTAINING DISAZO DYES FOR NYLON [52] US. Cl 260/186, 260/174, 260/177, 260/184 [51] Int. Cl. C09b 31/06, D06p 3/24 [58] Field of Search 260/186, 194, 177; l/l84 [56] References Cited UNITED STATES PATENTS 12/1969 Speck 260/186 FOREIGN PATENTS OR APPLICATIONS l,20l,549 12/1959 France 260/186 Primary ExaminerFloyd D. I-Iigel Attorney, Agent, or Firm-Joseph G. Kolodny; Edward McC. Robert; Prabodh I. Almaula [57] ABSTRACT Compounds of the formula A B on 1 H035 B E2 wherein A is hydrogen, lower alkyl, such as' methyl, ethyl, butyl or lower alkoxy, such as methoxy. ethoxy, butoxy, or chlorine; B is hydrogen, lower alkyl such as methyl, ethyl or butyl or lower alkoxy, such as methoxy, ethoxy or butoxy; B is lower alkoxy such as methoxy, ethoxy or butoxy; E, is hydrogen. lower alkyl such as methyl, ethyl, butyl or lower alkoxy such as methoxy, ethoxy or butoxy, E is hydrogen, lower alkyl such as methyl or ethyl, lower alkoxy such as methoxy or ethoxy; R is lower alkyl of l to 4 carbon atoms, such as methyl, ethyl, propyl or butyl and OR is either ortho or para to the azo linkage; and SO H is either meta or para to A, provide yellow to scarlet dyeings of very good fastness and dyeing properties and excellent leveling characteristics on natural and synthetic polyamide fibers.

11 Claims, No Drawings LOWER ALKYL EITHER-CONTAINING DISAZO wool and for dyeing artificial fibers of superpolyamides DYES FOR NYLON or superpolyurethanes. The dyeings obtainable therewith are distinguished by the purity, brightness and BACKGROUND OF THE INVENTION strength of their tints, by good properties of fastness to The use of monoazo-dyestuffs containing a sulfonic 5 alkali, light and washing, by good barre coverage and acid group for the dyeing of animal fibers and artificial by gOOd leveling and transfer properties.

fibers of superpolyamides or superpolyurethanes is The y of the Present invention Provide y g known. However, the dyeing of nylon presents particu- Over a Shade range from Yellow to lar r bl i bt i i d 1 li d h The dyes will also dye well in combination, especially achievement of optimum leveling is a very important f the use of a leveling ageht- If desired, a nvenconsideration in the dyeing or printing of nylon in order hohal after-treatment can be give" to the y milleto cover up irregularities. rial- The following examples illustrate the invention. SUMMARY OF THE INVENTION The present invention relates and has for its objects EXAMPLE I the provision of dyestuffs particularly suited for the coloring f nylon fib A. 17.3 g. of metanilic acid are dissolved in 70 g. of

In accordance with the present invention, it has been Water and '8- of 50 Percent y Weight caustic Soda found that valuable dyeings are obtained on natural lution. Ice, 22 g. of conc. hydrochloric acid, and asoluand synthetic fibers by the use as dyestuffs of disazo tion of 7 g. of sodium nitrite in 20 g. of water are added compounds of the formula with sufficient ice to maintain the temperature at no 3 B E2 1 wherein A is hydrogen, lower alkyl, such as methyl, 0-3C to diazotize the metanilic acid. ethyl, butyl or lower alkoxy, such as methoxy, ethoxy, B. 15.3 g. of 2,5-dimethoxyaniline, dissolved at 45C butoxy, or chlorine; B is hydrogen, lower alkyl such as in 120 g. of water and ll gfof conc. hydrochloric acid methyl, ethyl or butyl or lower alkoxy, such as mcthare combined with the diazotized metanilic acid, using oxy, ethoxy or butoxy; B is lower alkoxy such as methsufficient ice to keep the temperature below 5C and oxy, ethoxy or butoxy; E is hydrogen, lower alkyl such the pH is raised to 2.5 with 20 percent sodav ash soluas methyl, ethyl butyl or lower alkoxy such as methoxy, tion. After completion of the coupling, the product is ethoxy or butoxy; E is hydrogen, methyl, ethyl, methdissolved at pH 9 with 50 percent caustic soda solution oxy or ethoxy; R is lower alkyl of l to 4 carbon atoms, and then salted with 50 g. of sodium chloride. Rediasuch as methyl, ethyl, propyl or butyl and OR is either zotization is accomplished by addition of 7.5 g. of so ortho or para to the azo linkage; and SO H is either 40 dium nitrite, followed by an aqueous solution of 21 g.

meta or para to A. of naphthalenesulfonic acid and sufficient sulfuric acid The compounds of the present invention are preto establish a congo acid reaction. A temperature of pared according to known procedures by diazotizing 32C is maintained for 2 hours.

unsubstituted or properly ring-substituted metanilic or C, This reaction mass is added during one hour to a lllf i p g the dialotized POUHdS solution of 9.4 g. of phenol, 3 g. of caustic soda, and 25 with an arylamine such as alkoxy substituted aniline or g. of soda ash in 200 g. of water while the temperature its N-methane sulfonic acid, following with an alkali is held below 5C by addition of ice. The resulting treatment in case of N-methane-sulfonic acid, rediazotslurry is stirred for 2 hours, neutralized with hydrochloizing the p-aminoazo compound, coupling the rediazotric acid, and filtered.

iZed Product with a Phenolic compound Such as P D. The filter cake is charged into 250 g. of percent cresol or methoxy-phenol, followed by alkylation of the ethanol, g. of water, 8.5 g. of 50 percent by weight product to provide the novel dyestuff of the present inaqueous stic sod ol ti n, and 35 g, of oda ash in vention. an autoclave. 25 g. of ethyl chloride is pumped in and The dyestuffs of the P e lhvehllo" can e 55 the mixture is stirred for 20 hours at l l()C. It is then p y In the form o their saltsZ for p m the cooled, diluted to twice the volume with water, and fil-' form of the a flwm l j 0r fllkall metals, Such as tered. The filter cake is dried to give an orange waterdlum, potassium or lithium salts. l bl pr d t of the formula OCH SO 1 OCH3 The disazo-dyestuffs of the present invention have The product dyes nylon clear level shades of orange of good water-solubility and can be used for dyeing or good fastness properties. printing a very wide variety of materials, principally for r dyeing animal fibers such as leather, silk and especially EXAMPLE 2 The procedure of Example 1 is repeated except that in step C 12.4 g. of meta-methoxyphenol are employed in place of 9.4 g. of phenol.

The product obtained has the formula EXAMPLE 6 A. 17.3 g. of metanilic acid are diazotized employing the procedure set forth under Example 1 A).

B. The resulting diazotized metanilic acid is com- OCH and dyes nylon clear level shades of scarlet having good fastness properties.

EXAMPLE 3 The procedure of Example 1 is repeated except that in step D grams of methyl chloride are employed in place of g. of ethyl chloride.

The product obtained has the formula and dyes nylon clear and level shades of orange having good fastness properties.

OCH3

OCH

EXAMPLE 4 The procedure of Example 1 is repeated except that bined at a temperature below 5C with 13.7 g. of 2- methoxy-S-methylaniline previously dissolved in 120 g. of water at 45C and 1 l g. of concentrated hydrochlo ric acid. Sufficient 20 percent soda ash solution is added to raise the pH to 3.0 and the mixture is stirred for a period of five hours.

After completion of the coupling, the product is filtered off, redissolved in 500 g. of water at 50C with 8 g. of a 50 percent by weight caustic soda solution and salted with 28 g. of sodium chloride after cooling to 30 20C. Rediazotization is accomplished by addition of 7.2 g. of sodium nitrite, followed by an aqueous solution of 21 g. of naphthalenesulfonic acid and sufficient sulfuric acid to establish a congo acid reaction. One hour later an amount of sodium chloride equivalent to in step C 10.8 g. of o-cresol are employed in place of 3 5 20 percent of the volume of the slurry is added and the 9.4 g. of phenol.

The product obtained has the formula OCH 3 SO H CH and dyes nylon clear level shades of orange with good fastness properties.

EXAMPLE 5 OCH3 CH SOBH OCH3 OCZHS yielding clear level orange dyeings of good fastness properties.

slurry cooled to 8C. The precipitate is collected by filtration.

C. The precipitate from B is reslurred in 250 g. of cold water and the resulting slurry is added over one hour to a solution of 9.4 g. of phenol, 3 g. of caustic soda and 20 g. of soda ash in 200 g. of water while the temperature is held below 5C by the addition of ice. The product is salted with g. sodium chloride, stirred for 2 hours and filtered.

D. The filter cake is charged into 250 g. of percent ethanol, g. of water, 8.5 g. of 50 percent by weight aqueous caustic soda solution, and 35 g. of soda ash in an autoclave. 25 g. of ethyl chloride is pumped in and the mixture is stirred for 20 hours at l 10C. It is then cooled, diluted to twice the volume with water, and fl]- tered. The filter cake is dried to give an orange watersoluble product of the formula The product dyes nylon level shades of dull orangeyellow having good fastness properties.

EXAMPLE 7 The procedure of Example 6 is repeated except that in step C 10.8 g. of o-cresol are used in place of the 9.4

g. of phenol.

The product obtained has the formula OCH and dyes nylon clear level shades of yellow-orange of good fastness properties.

EXAMPLE 8 The procedure of Example 6 is repeated except that in step C 12.4 g. of meta-methoxyphenol are used in place of the 9.4 g. of phenol.

The product obtained has the formula OCH The coupling product is then acidified to a pH of 1.5 and isolated by filtration. The product is dissolved in 10 250 g. of water at 50C with sufficient caustic soda to raise the pH to 8.0. To this solution there is added 7.2 g. of sodium nitrite together with 10 g. of sodium naphthalenesulfonate. The resulting reaction mixture is then gradually added to 200 g. of water containing 15 g. of concentrated hydrochloric acid and the mixture 0 H CH OCH3 and dyes nylon clear level shades of reddish-orange of good fastness properties.

EXAMPLE 9 A. 17.3 g. of sulfanilic acid are diazotized in g. of ice-water and 11 g. of concentrated hydrochloric acid H033 -0- N=N by the rapid addition of a concentrated solution of 7 g. of sodium nitrite in water at about 4C.

B. The resulting diazotized sulfanilic acid is combinecl at a temperature below 5C with 13.7 g. of 2- methoxy-S-methylaniline previously dissolved in 120 g. of water at 45C and 11 g of concentrated hydrochloric acid. Sufficient 20 percent soda ash solution is added ethanol, g. of water, 8.5 g. of 50 percent by weight aqueous caustic soda solution, and 35 g. of soda ash in an autoclave. 25 g. of ethyl chloride is pumped in and the mixture is stirred for 20 hours-at C. It is then cooled, diluted to twice the volume with water, and filtered. The filter cake is dried to give an orange watersoluble product of the formula The product dyes nylon clear level shades of ye]- loworange of good fastness properties.

EXAMPLE 10 The procedure of Example 9 is repeated except that in step C 10.8 g. of o-cresol are employed in place of to raise the pH to 3.0 and the mixture is stirred for a pe- 60 9.4 g. of phenol.

riod of five hours.

The product obtained has the formula OCH 3 CH3 and dyes nylon clear level shades of yellow-orange of good fastness properties.

EXAMPLE 1 l The procedure of Example 9 is repeated except that 5 in step C 12.4 g. of guaiacol are employed in place of 9.4 g. of phenol.

The product obtained has the formula OCH3 and dyes nylon clear level shades of yellow-orange of good fastness properties.

EXAMPLE 12 A. 17.3 g. of metanilic acid are diazotized by the procedure set forth in Example 1 A).

B. The pH of the resulting solution is adjusted to 2.5 by addition of sodium bicarbonate. 6.6 g. of sodium acetate is added, followed by the addition of 22.5 g. of o-anisidyl-N-methanesulfonic acid, while maintaining the temperature of the reaction mixture at about 5-7C by means of ice and cold water and stirring for a period of 1 hour. 38 g. ofa 50 percent by weight solution of caustic soda are then added and the mass is heated at 100C for 8 hours. The mass is then cooled, 28 g. of sodium bicarbonate are added to adjust the pH to 9, salted with 33 g. of sodium chloride and filtered.

The filter cake is dissolved in 800 g. of water at 30C.

To this solution there is added 7 g. of sodium nitrite, followed by addition of an aqueous solution of 21 g. of naphthalenesulfonic acid and sufficient sulfuric acid to establish a congo acid reaction and the mixture maintained at 32C for a period of 2 hours.

C. The mixture from B is added during a 1 hour period to a solution of 9.4 g. of phenol, 3 g. of caustic soda and 25 g. of soda ash in 200 g. of water while the OCH 3 temperature is held below 5C by the addition of ice.

The product dyes nylon clear level shades of yellow of good fastness properties.

Following the general procedure above and employ- 40 ing the corresponding reactants the compounds below are prepared providing the indicated shade.

EXAMPLE I3 Example 1 1.

Example 15.

N=N (dull yellow) Z S (yellow-oral?) EXAMPLE 16 fonic acid and sufficient sulfuric acid to establish a congo acid reaction. Three hours later this reaction mass is added during one half hour to a solution of 9.4

20.3 g. of 3-amino-4-methoxybenzene sulfonic acid g. of phenol, 3 g. of caustic soda, and 35 g. of soda ash are neutralized in 125 g. of water with 8 g. of 50 per- 5 in 200 g. of water while the temperature is held below cent by weight caustic soda solution. Insoluble matter 5C by addition of ice. After stirring for two hours the is then removed by filtration. The clear solution is acidpH is reduced to 8.0 with hydrochloric acid and the ified with 22 g. of conc. hydro chloric acid and diazo product is collected on a filter funnel. tized at O3C by rapid addition of 7 g. of sodium ni- The filter cake is ethylated in an autoclave by the trite in 20 g. of water, and of ice. 1O procedure of Example 1 D). The product obtained has It is then combined with 13.7 g. of Z-methoxy-S- the structure ocI-t H N=N OC H 03H CH3 methylaniline by the procedure set forth in Example 6. and dyes nylon clear level shades of yellow-orange.

The coupling product is filtered off the next morning, Following the procedure set forth in Example 16 and dissolved in 800 g. of water containing 4 g. of caustic employing the corresponding reactants the compounds soda, and salted with g. of sodium chloride. 7 g. of below are prepared, providing the indicated shade.

Example 17.

003 OCH CH orange-brown) S0 CH OC H Example 18.

OCH OCH (brownish- SO H H 3 3 orange) sodium nitrite are added, followed after cooling to The following examples illustrate further-but by no 12C by an aqueous solution of 30 g. of naphthalenesulmeans limitthe scope of this invention.

Example 19.

OCH

N= N=N OCH 3 (scarlet) SO31! OCH?) OCH3 Example 20.

OCH w=n-u=n0ocn (yellow) S0 11 Example 21 0on CH N=N Oren G- oc n I claim: 1. A compound of the formula g 5) H 5 B and SO M is meta or para to the azo linkage.

3. A compound according to claim 2 of the formula OR N= N=N 5 wherein M is H, Na, K or-Nl-L; R is H, CH Cl or -OCH R is H or Cl-l R is -H or ---CH;,;

OR is ortho or para to the azo linkage and SO M R5 is or H is meta or para to A.

2. A compound of the formula R is H, or CH;,, R is H or CH;,, R is CH or Cl-I CH OR is ortho or para to the azo linkage OCH 0R is ortho or para to the azo linkage and -SO M is meta or para to the azo linkage.

4. A compound according to claim 3 of the formula 5. A compound according to claim 1 having the formula 6. A compound according to claim 1 having the for- 9. A compound according to claim I having the formula mula 0CH Piniflmg 00 11 S OCH OCH 0011 7 Qua: N=N 00 11 0 50 1-1 OCH 7. A compound according to claim 1 having the for- 10. A compound according to claim 1 having the formula mula 0CH Qua N=N -OOCH SO H OCH OCH CH3 QM GM OOC H SO 3 8. A compound according to claim 1 having the for- 11. Acompound according to claim 1 having the formula 45 mula 0CH CH QN-m N=N SO 3 OCH 0C H C1 OCH OCH OCH3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,862,119

DATED 1 January 21, 1975 INVENTORt'S) 1 HANS ALFRED STINGL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In claim 3, in the structural formula, delete "R so the central ring reads Signed and sealed this 27th day of May 1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks 

2. A compound of the formula
 3. A compound according to claim 2 of the formula
 4. A compound according to claim 3 of the formula
 5. A compound according to claim 1 having the formula
 6. A compound according to claim 1 having the formula
 7. A compound according to claim 1 having the formula
 8. A compound according to claim 1 having the formula
 9. A compound according to claim 1 having the formula
 10. A compound according to claim 1 having the formula
 11. A compound according to claim 1 having the formula 